Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
  • C09D191/06—Waxes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

• the present invention relates particularly to organic coating compositions and methods for their use generally classified in Class 106, particularly in Subclasses 14.11, 14.13, 14.15, 14.16, 14,34, 14.35, 14.37, 14.38, 270, 271 and 272.
• U.S. Patent 3,539,367 to Yaroshevich, et al discloses a wax emulsion containing a salt of an organic acid and an amine.
• U.S. Patent 3,660,128 to Sheldahl teaches an alkanolamine and an aliphatic carboxylic acid in the preparation of a semi-solid wax-in-water emulsion.
• U.S. Patent 2,349,326 to Wilson teaches a combination of morpholine and a fatty acid to emulsify waxy materials in water for paste-type waxes.
• U.S. Patent 3,125,453 to Simmonds employs a mixture of triethanolamine and an acid to emulsify a mixture of waxes also for paste-type polishes.
• U.S. Patent 4,035,514 to Davis teaches a water-dispersable petrolatum composition containing cetyl alcohol, lanolin alcohols and alkoxylate fatty acid esters of sorbitol.
• the present invention possibly through the use of co-solvents which tend to form azeotropes which enhance water removal during curing, provides coatings having substantial life even in corrosive environments. While not wishing to be bound to any theory or mechanism, it appears the co-solvents tend to act as dispersing agents and additionally enhance stability of the liquid compositions at low temperatures.
• the inclusion of the salts of organic acids in the present invention tend to build longer-chain molecules which additionally deter corrosion and promote stability.
• the coatings of the present invention find additional utility as lubricants, e.g. particularly for wire drawing and other metal drawing, extrusion and impact forming operations.
• the coating compositions of the present invention are water-borne, storage stable, even at higher temperatures, and provide coatings which usually are semi-firm but non-tacky, which can be light in color, which have low odor levels, which display enhanced corrosion prevention and which can be formulated to be readily removable in hot (e.g. 60°C+) water.
• the present invention relates to water-borne coating compositions of high temperature (e.g. 52°C) storage stability which, when applied to a substrate, usually form a soft but non-tacky, flexible, hot water removable, low odor, lubricating, corrosion preventative film capable of being formulated in light colors.
• high temperature e.g. 52°C
• the coating compositions of the present invention which are capable of application and flow onto a solid substrate, and comprise: (1) usually one or more waxes, (2) one or more organic esters, (3) one or more surfactants, (4) one or more coupling agents many of which are carefully selected to result in final dispersion stable at higher temperatures and (5) water; to form a water-borne dispersion for greatly improved corrosion resistance, especially when employed as a long-term metal preservative.
• the invention provides valuable coating formulations having excellent corrosion protection and storage stability.
• compositions of the present invention will include semirefined paraffin wax having a melting point of below about 60°C and preferably 50 0 C which contains about 10 to about 30 and more preferably 15 to about 25 weight percent oil based on the weight of the paraffin wax though other types of wax may occasionally be substituted for specialized applications.
• General paraffin waxes can be naturally derived, e.g. those manufactured in the processing of petroleum crude oils, or synthetically manufactured, e.g. polyolefin waxes such as polyethylene or polypropylene waxes.
• the average molecular weight of the waxes useful in the present invention should be selected so as to provide good removability, but molecular weight is not narrowly critical and will be easily selected by those skilled in the art.
• the degree of branching in the wax molecules should be selected so the average degree of crystallinity permits the wax to be easily dispersed and to be compatable with the other ingredients of the particular formulation being produced.
• Chain branching provides sites for esterification in the case of oxygenated waxes; these are also suitable for use in most applications with the present invention.
• Oxygenated waxes will preferably have an acid number in the range of from about 15 to about 200, most preferably from 25 to about 45.
• the wax composition can contain 10 to 50, more preferably 15 to 35 and most preferably 20 to 30% of a hydrocarbon oil, preferably saturated.
• Specific waxes useful for the present invention include: natural waxes, such as slack wax, a semirefined paraffin available from Penreco Co. of Butler, Pennsylvania; petrolatum, widely available; synthetic waxes, such as polyethylene waxes available from Bareco Corporation of Tulsa, Oklahoma or the Epolene brand available from Eastman Kodak of Rochester, New York or oxygenated waxes, such as oxidized petrolatum which can be readily manufactured in petroleum refineries utilizing well-known techniques. Also useful are those available from Durachem Corporation of Harrison, New York. Others include: Polywax 55 (Bareco) and Mobil Microwax 2305 (Mobil Oil).
• the amount of waxes to be utilized with the present invention is not narrowly critical and, in fact, for special applications the wax can even be omitted with additional quantities of the esters described below being employed.
• the wax content will be from 0.5 to 30%, more preferably from about 5 to 25% and most preferably from about 12 to about 20% by weight.
• the esters useful for the present invention are preferably polyfunctional esters of carboxylic acids, preferably of fatty acids having 6 to 30 carbons. Mono-esters may find occasional use in special circumstances. Particularly preferred are the polyesters of naturally-derived fatty acids such as organic acid esters of glycerine, coconut oil, tall oil, soya oil acids, stearic acid, preferably, isostearic acid, oleic acid, and polyols, e.g. neopentylglycol, trimethylol propane and pentaerythrol. Most preferred is the dilanolinic acid ester of pentaerythritol.
• Useful commercial polyol esters comprise: "P-entalan” from Croda Chemical Company of England, a tetrahydric lanolin alcohol; Degras manufactured by Emory Industries of Linden, New Jersey and FAI manufactured by Arizona Chemical of New York City.
• Table I illustrates the starting materials for a number of suitable esters.
• Esters II and II have small amounts of insoluble resins - these were filtered out.
• Adjustment of residual acid number for esters up to 25 is made with oxwax.
• esters employed with the present invention will not be narrowly critical and will depend to a substantial degree on the other ingredients and their amounts as selected for the particular formulation.
• the compositions will contain from about 1% to about 30%, more preferably from about 5% to about 10% and most preferably from about 8% to about 12% percent esters based on the total weight of the esters as compared to the total weight of the formulation.
• Surfactants useful with the present invention include natural surfactants such as salts of oleic acid, e.g. morpholine salts of oleic acid, or the similar salt of triethanolamine and entirely synthetic surfactants such as alkanol amide, e.g. WHC by Stepan Chemical Company of Chicago, Illinois (oleyl diethanol amide), sorbitan mono-oleates manufactured by ICI America of Wilmington, Delaware, isostearic acid salts, coconut oil salts, lauric acid salts and the like. Excess carboxylic acid, e.g. in the wax components, can react with amines in situ to form salts which act as surfactants. All or part of the surfactant can be organic sulfonates, e.g. alkyl lauryl sulfonate or alkyl benzene sulfonates.
• Suitable surfactants comprise the reaction products of amines such as morpholine, triethanolamine, ammonia, diethanolamine and triethanolamine with carboxylic acids such as those mentioned above.
• the compositions of the present invention will generally include surfactants in the amount of from about 0.5 to about 6, more preferably from about 3 to about 5 and most preferably from about 3 to about 4 percent by weight based on the weight of the formulation. However, this will vary in response to the selection and quantities of the other ingredients employed.
• coupling agents can be employed with the invention including mineral spirits, e.g. ethylene glycol ethers, preferably butyl and propyl ethers; hydroxy ethers (ether-alcohols), such as butyl cellosolve, (Ektasolve EP manufactured by Eastman Kodak of Rochester, New York), sorbitan (mono-ester of sorbitol) diethylene glycol monoethyl ether, monopropyl ether, of ethylene glycol, propyl cellosolve, ethyl cellosolve, and diethylene glycol monoethyl ether, and other coupling agents which will be evident to those skilled in the art for use in specialized formulations according to the present invention.
• the coupling agent is selected by physical test; anything which does not interfere with the formulations of the present invention and which renders their ingredients mutually soluble in the water base will generally be acceptable.
• Alcohol ether-esters may also be used e.g. ethylene glycol monoacetate, diethylene glycol monoproprionate, diethylene glycol monoacetate, and propylene glycol monoacetate.
• Alcohols such as ethanol, isopropanol and isobutanol will generally be useful as coupling agents for the invention.
• Other commercial coupling agents which are useful with formulations of the present invention include: Ektasolve EP, manufactured by Eastman Kodak of New York, and Propasol P, manufactured by Union Carbide of Danbury, Connecticut.
• the coupling agents of the present invention will generally be employed in quantities of from about 1%_ to about 15% or more, more preferably from about 3 to about 12%, and most preferably from about 4 to about 10% based on the weight of the formulation.
• the coupling agent will usually be useful during the drying and curing process after application of the coatings composition of the present invention to substrates. For example, when carefully, selected, the coupling agent will form an azeotrope with the water present in the formulation, thus increasing volatility, speeding cure, and providing a more permanent coating.
• Some coupling agents will assist the final coating in other ways, e.g. by providing leveling of the final coating, avoiding pinholes and providing a more continuous, better quality dry film.
• Deionized water will preferably be employed with the formulations of the present invention in order to prevent reaction of chlorine, calcium, magnesium or other components of tap water from interfering with the formulations or their curing. Distilled water could, of course, be employed but will generally be avoided for economic reasons.
• Formulations of the present invention will generally contain a minimum of about 45%, more preferably 50% and most preferably 60% or even more of water based on the total weight of the formulation.
• a quantity of water greater than about 92% may cause swelling and loss of wetting properties in most of the formulations of the present invention although specialized formulations utilizing carefully selected non-aqueous ingredients may tolerate water up to an amount of 97% by weight based on the weight of the total formulation.
• the pH of this system will be preferably in the range of 7.0-10 with 8.0-9.0 being preferred.
• the nature of the emulsion will depend heavily upon the amount of soap produced when the emulsifying agent (fatty acid) is neutralized with an alkaline material (e.g. amines, triethanolamine, morpholine).
• an alkaline material e.g. amines, triethanolamine, morpholine.
• the apparatus for the present invention will be that conventionally utilized in the preparation of coatings compositions, e.g. kettles and mixing tanks having flow metering or measuring devices and agitation means, e.g. pumps mounted on side-arms connecting with the main vessel, internal stirrers, contra-rotating shearing devices and any of the other available devices which are well known to the art.
• flow metering or measuring devices and agitation means e.g. pumps mounted on side-arms connecting with the main vessel, internal stirrers, contra-rotating shearing devices and any of the other available devices which are well known to the art.
• the temperature during mixing may be different during different stages in the formulation.
• the water will be at about 200°F (93°C)
• the non-aqueous ingredients will be transferred and mixed together at about 225°F (107°C).
• these temperatures are not narrowly critical and will vary to provide faster mixing or better compatability of ingredients according to observation of those skilled in the art.
• pressure vessels may be utilized for the purpose of lowering ingredient melting and boiling points, where useful, in order to provide better dispersion of difficult-to-mix ingredients.
• the formulations of the present invention may be manufactured continuously if desired, batch techniques will be more usually employed.
• the total amount of water desired in the finished formulation e.g. 1700 gallons, 6,562 liters
• the wax, if any, esters, surfactants, coupling agents and any other non-aqueous ingredients are heated in a separate vessel until the temperature reaches about 225°F (107°C) with the various non-aqueous ingredients being added slowly while the vessel is agitated with conventional mixer.
• the esters will be added with the carboxylic acids; the neutralizing ingredient, e.g.
• the non-aqueous ingredients are allowed to mix for 15 to 30 minutes and transferred over to the aqueous phase, which is agitated during the addition of the non-aqueous phase. Heating is discontinued after addition of the non-aqueous phase, and the finished formulation is allowed to cool with, preferably, constant agitation, after which the formulation is drawn off into shipping containers, e.g. tank cars, tank trucks, drums or smaller cans.
• shipping containers e.g. tank cars, tank trucks, drums or smaller cans.
• the finished formulation prior to packaging, will generally be checked for pH, solids content, freeze-thaw stability, corrosion-protection under accelerated conditions and other tests utilizing techniques well known to the coatings industry.
• the formulations of the present invention may be applied to substrates to be protected by conventional application techniques, such as spraying, brushing, roller-coating, dipping, flow-coating, electrostatic airless spraying.
• Coating- thickness can be varied by changing the formulation, the number of coats, or the amount applied per coat but in general will be in the range from about 0.5 to about 3 mils per coat after drying.
• Heating is then terminated and the mixture continuously agitated until it cools to 100°F (38°C).
• the pH is then adjusted to 8.5 by addition of less than one part of morpholine. About three parts of water are added to compensate for water lost during heating. The solids content is then found to be about 30%.
• the resulting product is tested for corrosion resistance by applying to a cold rolled 1010 steel panel. After drying for 72 hours the test panel is subjected to a 5% salt (NaCl) spray at a temperature of 95°F (35°C) according to ASTM test B-117. The test panel resists failure (corrosion) for 500 hours.
• a 5% salt NaCl
• a similar test panel coated with the formulation of this example I resists 2,000 hours of exposure to 100% relative humidity at 120°F (44°C) according to the techniques of ASTM D-2247.
• a sample of the above formulation survives five successive freeze-thaw cycles each comprising 16 hours at 0°F (-18°C) followed by eight hours at 77°F (25°C) with no separation or other evident deleterious effect.
• a sample of the above formulation withstands 144 hours at 120°F (49°C) without separation or other observable deleterious effect..
• the thickness on the above test panels is approximately 0.8 mil (approximately 20 microns or 0.20 millimeters).
• Example IV This is a formulation produced according to techniques set forth above for Example I, except that 25% more pentaerythritol dilanolate (note: residual acid is #10, Sap. is #170) is substituted for 25% slack wax, 8% butyl cellosolve is substituted for 5% Ektasolve-EP, and no oleic acid is present.
• the film properties are similar to the best mode (Example I), but the cost is much greater.
• Example V This is a formulation produced according to techniques set forth above for Example I, except that 10% of the total 330 slack wax is replaced by 5% pentaerythritol dilanolate plus 5% Mobil Micro Wax, and the 5% Ektasolve-EP is replaced by 5% mineral spirits. This formulation had inferior emulsibility and poorer film properties, probably due to interactions of the components.
• Example VI This is a formulation produced according to techniques set forth above for Example V except that the 10% of 330 slack wax is replaced by 10% of Degras lanolin (residual:acid #7-10). This formulation performed comparably to that of Example V.
• Example VII This is a formulation produced according to techniques set forth above for Example I, except that the 25% of 330 slack wax and 5% of the water is replaced by 20% Mobil Microwax and 10% pantaerythritol lanolate.
• Example VIII This is a formulation produced according to techniques set forth above for Example I, except that 3% of oleic acid is replaced. by 3% of Stepan WHC. Processing and film properties, while acceptable, are inferior to the best mode. This is especially true water sensitivity of the film.
• the formulations of the invention can be prepared as concentrates to which a substantial amount of water can be added in order to avoid shipping of water, particularly for international or other long distance shipment.
• the formulations may contain other useful ingredients such as biocides, antifoam agents, pigments, dyes and leveling agents, well known to those skilled in coatings technology.

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• 1982
  • 1982-05-03 US US06/374,466 patent/US4444803A/en not_active Expired - Fee Related
• 1983
  • 1983-04-27 EP EP19830104107 patent/EP0093388A3/de not_active Withdrawn
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